Imperial College

4I10 Green Chemistry London

Lecture 2: Green Metrics

4.I10 Green Chemistry Lecture 2 Slide 1

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From the end of last week’s lecture London

Green Chemistry is often said to be a 'cradle to grave' approach. Explain

what this term means with specific reference to the industrial production
of polyethylene.
5 marks

‘Cradle to grave’ describes the need to consider ALL factors in the

production of a chemical from the source of the raw materials, to the
disposal / recycle of the product once its useful lifetime has ended.

Possible factors might include:

• ethylene is produced from petroleum feedstocks (is biomass an
alternative, renewable source?)
• catalysts greatly reduce the temperature and pressure conditions
• no solvents are used (gas phase monomer passed over a solid
catalyst)
• minimal waste
• polyethylene is non-degradable, therefore it contributes significantly
to landfill; recycling is difficult and energy intensive
• energy requirements, transportation to market etc.
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Lecture 2: Learning Objectives London

By the end of today's lecture you should be able to:

(i) discuss (but not memorise) the 12 Principles of Green Chemistry;

(ii) calculate Atom Economies, E-factors and Effective Mass Yields for
chemical processes;

(iii) discuss the advantages and disadvantages of each approach;

(iv) describe the competing processes for the industrial production of

• dimethyl carbonate

• lactic acid

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Today’s lecture London

How can we measure the ‘greenness’ of a chemical reaction?

OR, given two chemical processes, how can we decide which

is most consistent with the Principles of Green Chemistry?

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The Twelve Principles of Green Chemistry: 1-6 London

1) It is better to prevent waste than to treat or clean up waste after it is

formed.

2) Synthetic methods should be designed to maximize the incorporation

of all materials used in the process into the final product.

3) Wherever practicable, synthetic methodologies should be designed to

use and generate substances that possess little or no toxicity to
human health and the environment.

4) Chemical products should be designed to preserve efficiency of

function, whilst reducing toxicity.

5) The use of auxiliary substances (e.g. solvents, separating agents etc.)

should be made unnecessary wherever possible and innocuous when
used.

6) Energy requirements should be minimized. Synthetic methods should

be conducted at ambient temperature and pressure.
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The Twelve Principles of Green Chemistry: 7-12 London

7) A raw material or feedstock should be renewable rather than depleting

wherever technically and economically possible.

8) Unnecessary derivatisation (blocking group, protection/deprotection,

temporary modification) should be avoided whenever possible.

9) Catalytic reagents are superior to stoichiometric ones.

10) Chemical products should be designed so that at the end of their

function they do not persist in the environment and break down into
innocuous degradation products.

11) Analytical methodologies need to be further developed to allow for

real-time in-process monitoring and control prior to the formation of
hazardous substances.

12) Substances used in a chemical process should be chosen so as to

minimize the potential for chemical accidents, including releases,
explosions and fires.
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The Twelve Principles of Green Chemistry: Summary London

Reduction in: 1 2 3 4 5 6 7 8 9 10 11 12

Materials

Waste

Hazards

Toxicity

Environmental impact

Energy

Cost

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Two syntheses of dimethyl carbonate - which is greener? London

1. Traditional synthesis from phosgene and methanol

phosgene

2. Modern synthesis - methanol carbonylation

Route 2 is preferred since it avoids the use of phosgene and it gives less
harmful side-products (route 2 also produces purer product, so energy
intensive purification steps are eliminated).

Some decisions are straightforward

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Two syntheses of lactic acid (HOCHMeCO2H) - which is greener? London

1. Chemical – hydrocyanation of acetaldehyde

1. Biochemical – fermentation of sugars or starch

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Two syntheses of lactic acid (HOCHMeCO2H) - which is greener? London

Chemical synthesis from CH3CHO and HCN

Reactor 1: hydrocyanation; 2: hydrolysis; 3: esterification; 4: hydrolysis

MeCH(OH)CN MeCH(OH)CO2Me

high purity
MeCH(OH)CO2H
distillation column

distillation column

distillation column
low purity
HCN 'technical grade'
MeCH(OH)CO2H
1 2 3 4
CH3CHO MeOH

H2SO4 H2O MeOH H2O

(NH4)2SO4
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Biochemical (fermentation) route to lactic acid London

Biosynthesis from starch

Reactor 1: fermentation; 2: salt formation; 3: filtration; 4: hydrolysis
H2O

evaporation column
CaCO3

fermentation broth calcium lactate H2SO4

corn including
starch MeCH(OH)CO2H
1 2
3
4
technical
grade
lactobacillus lactic acid
acidophilus, H2O
solid waste
filtered off CaSO4

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Chemical synthesis of lactic acid London

Advantages
• Fast, high yielding reactions.
• MeOH generated in final step is recycled.

• Produces high purity lactic acid (> 99 %).

Disadvantages
• HCN is highly toxic; CH3CHO and MeOH are also toxic.
• Waste stream of (NH4)2SO4 produced (can be used as a fertiliser).

• Several energy intensive distillations required

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Biochemical synthesis of lactic acid London

Advantages
• Renewable feedstocks.
• Uses non-hazardous materials.

Disadvantages
• Slow (every cycle takes 4-6 days).
• Quantity of product per reactor volume is low.

• Evaporation is required (due to low salt concentration) -

energetically intensive.

• Technical grade lactic acid (ca. 85 % purity) produced. In order to

produce high purity product, the material still has to undergo the
methanol transesterification process outlined on slide 10.

• Waste stream of CaSO4 produced and very large quantities of

waste water.
Some decisions are more difficult!
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So how can we make such decisions easier? London

In order to try to decide which chemical process is greener, chemists have

tried to develop ways of measuring ‘greenness’.

The two most common methods are called:

• Atom Economy;

• E-factor.

Both methods concentrate on reducing waste – other factors

(e.g. toxicity, risks, energy consumption etc) are ignored.

The only true way to decide between two reactions is to perform

a full life cycle analysis (e.g. the nappies question in lecture 1).

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Traditional way of comparing reactions - percentage yields London

Isolated moles of product

Percentage yield = x 100 %
Theoretical maximum moles of product

However, percentage yield takes no account of by-products,

e.g. Wittig reaction:

86 % yield

FW = 98 96 278

∴ 1 kg C6H10O 842 g C7H12 2446 g Ph3PO

+
(10.2 mol) (8.8 mol) (8.8 mol)

This reaction is high yielding but produces a large amount of waste

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The Concept of Atom Efficiency and Atom Economy London

Atom Efficiency:
Synthetic methods should be designed to maximise the incorporation
of all materials used in the process into the final product.

FW of desired product(s)
Atom Economy = x 100 %
Combined FW of starting materials

e.g Wittig reaction:

96
Atom economy = = 25.7 %
98 + 276

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Atom efficient reaction classes London

Rearrangements (100% atom economy)

Claisen
rearrangement

Additions (100 % atom economy)

Hydrogenation

Carbonylation

Other examples include: Markownikoff additions,

Michael additions etc

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Atom efficient reaction classes London

Cycloadditions, e.g. Diels-Alder (100% atom economy)

273
62.5
363

40
FW = 66
"Aldrin"
Overall atom economy = 363 / (66 + 62.5 + 40 + 273)
= 82.2 %

Oxidations
32 120
122
18

Atom economy = 120 / (122 + 16) = 87.0 %

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Atom inefficient reaction classes London

Substitutions

Eliminations

Wittig reaction
see earlier slides

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E-Factors London

kgs of waste produced

E-factor =
kgs of desired product

Industry sector Annual production Total waste E-Factor

(tonnes) (tonnes)

Oil refining 106 - 108 106 ca. 0.1

Bulk chemicals 104 - 106 105 < 1-5
Fine chemicals 102 - 104 104 5 - >50
Pharmaceuticals 10 - 103 103 25 - >100

Advantages:
• take into account solvent use
Disadvantages:
• what if large volumes of solvent are water, or if the waste
consists of dilute aqueous solutions of benign inorganics?

• still concentrates on waste rather than other Green factors

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Atom economies and E-factors are usually in agreement London

1. Stoichiometric oxidation (Jones Reagent)

atom economy = 42 %
E-factor = ca. 1.5

2. Catalytic oxidation

atom economy = 87 %
E-factor = ca. 0.1

Principles of Green Chemistry: No. 9:

“Catalytic reagents are superior to stoichiometric ones.”

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Defficiencies of atom economies and E-factors London

Atom economies are a useful way of comparing

the waste production of alternative pathways,
but other factors should still be considered.

• Atom economies are theoretical and tell us nothing about reaction

yield or selectivity, or the nature (toxic / benign) of the waste stream.

• Atom economies only take into account stoichiometric reagents -

what about catalysts and solvents?

• Clearly, atom economies also tell us nothing about other green

chemistry concerns, e.g. energy, toxicity.

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Effective Mass Yield - EMY London

mass of desired product

EMY = x 100 %
mass of non-benign reagents

e.g. esterification of n-butanol with acetic acid

69 % yield
37g 60g 40g

EMY = (40 / 37) x 100 % = 108 %

The main disadvantage of this approach:

How do we judge if a reagent is non-benign?

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A final example London

e.g. esterification of n-butanol with acetic acid

Typical procedure: 37g butanol, 60 g glacial acetic acid and 3 drops of H 2SO4
are mixed together. The reaction mixture is then poured into 250 cm 3 water.
The organic layer is separated and washed again with water (100 cm 3),
saturated NaHCO3 (25 cm3) and more water (25 cm3). The crude ester is then
dried over anhydrous Na2SO4 (5 g), and then distilled. Yield = 40 g (69 %).

Metric Value Greenness

yield 69 % Moderate
atom economy 85 % Good (byproduct is water)
E-factor 502 / 40 = 12.6 Moderate
EMY 40/37 x 100 = 108 % Very good

EMY indicates that this reaction is very 'green'

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 Imperial College
Lecture 2 learning objectives - you should now be able to: London

(i)discuss (but not memorise) the 12 Principles of Green Chemistry

(ii) calculate Atom Economies, E-factors and Effective Mass Yields

FW of desired product(s)
Atom Economy = x 100 %
Combined FW of starting materials

kgs of waste produced

E-factor =
kgs of desired product

mass of desired product

EMY = x 100 %
mass of non-benign reagents

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Lecture 2 learning objectives - you should now be able to: London

(iii) discuss the advantages and disadvantages of each approach

Atom economies – simple to calculate, but focus too much on waste

E-factors – account for solvent use, but still focus principally on waste

EMY – account for toxicity of reagents, but the calculation is open to abuse

(iv) describe the competing processes for the industrial

production of dimethyl carbonate and lactic acid.

Dimethyl carbonate: phosgene versus methanol carbonylation

Lactic acid: chemical versus biosynthesis

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Green Metrics - Final words London

Recall the question of disposal versus renewal nappies from Lecture 1.

Trying to evaluate an entire production process is often an enormous and
complex task.

Instead, when questioning the sustainability of competing chemical

reactions we tend to compare the nature of five individual components:

• raw materials
• reaction types (e.g. additions, eliminations etc)
• reagents (e.g. catalysts)
• reaction conditions (including solvents)
• toxicity of products (including waste by-products)

The only complete answer comes from a life cycle analysis

Remember Lecture 1 - "Green Chemistry is not easy!"

The difficulties encountered in trying to measure
‘greenness’ are a major reason.

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Exam style question - answer next time London

Maleic anhydride may be prepared using two routes:

Oxidation of benzene:

Oxidation of but-1-ene:

The benzene oxidation route typically occurs in 65 % yield, while the but-1-
ene route only gives yields of 55 %.

(a) Assuming that each reaction is performed in the gas phase only, and that
no additional chemicals are required, calculate (i) the atom economy and (ii)
the effective mass yield of both reactions. You should assume that O 2, CO2
and H2O are not toxic.

(b) Which route would you recommend to industry? Outline the factors which
might influence your decision.
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